KR20100017170A - New metal precursors for semiconductor applications - Google Patents

Abstract

Methods and compositions for depositing metal films are disclosed herein. In general, the disclosed methods utilize precursor compounds comprising gold, silver, or copper. More specifically, the disclosed precursor compounds utilize pentadienyl ligands coupled to a metal to increase thermal stability. Furthermore, methods of depositing copper, gold, or silver are disclosed in conjunction with use of other precursors to deposit metal films. The methods and compositions may be used in a variety of deposition processes.

Description

New metal precursors for semiconductor applications {NEW METAL PRECURSORS FOR SEMICONDUCTOR APPLICATIONS}

The present invention generally relates to the field of semiconductor manufacturing. More specifically, the present invention relates to novel precursors for depositing metal films on substrates.

ALD and CVD are particularly useful techniques for the deposition of metal films in comparison with other deposition methods, for example physical deposition methods (PVD) such as sputtering, molecular beam epitaxy, ion beam implantation. ALD and CVD can also be used to provide flexibility in the design of electronic device manufacturing, including the possibility of reducing the number of processing steps required to deliver the desired product. These techniques enable selective deposition to deposit conformal deposits, copper, silver, gold and other materials. Suitable methods for forming metal films require identification of suitable precursors that require stringent requirements to be thermally stable, readily vaporized, reactive and cleanly degraded.

The demand for high performance interconnect materials is increasing as device shape size shrinks and device density increases. Copper has an ultra large scale integrated (ULSI) due to its low resistivity (Cu is 1.67 μΩcm, Al is 2.65 μΩcm), high electron transfer resistance and high melting point (Cu is 1083 ° C, Al is 660 ° C). ) Provides an alternative to CVD of aluminum in the device. Low interconnect resistivity can also enable faster devices.

Copper precursors are quite volatile and exhibit low deposition temperatures, but are very sensitive to heat and oxygen. The latter precursor is somewhat stable but is isolated as a high melting point solid and therefore requires a high deposition temperature. When using certain organometallic precursors, it is common for impurities such as carbon or oxygen to be incorporated during the thermal CVD process. For example, (η 5 -C 5 H 5) Cu (PMe 3) produces a copper film that leads to the incorporation of phosphorus. In addition, phosphine containing molecules are unsuitable due to their high toxicity. Organic phosphines are very toxic and PF3 is toxic and can cause unwanted phosphorus contamination and fluorine induced etch / damage. Thus, such chemicals may be subject to strict limitations.

Examples of conventional copper precursors include (1,1,1,5,5,5-hexafluoro-2,4-pentanedionate) CuL ((hfac) CuL), where L is a Lewis base. This type of precursor has been the most studied copper precursor to date because it can deposit copper through thermal disproportionation. In particular, (1,1,1,5,5,5-hexafluoro-2,4-pentanedionate) Cu (trimethylvinylsilane) is of great interest because it is a liquid having a moderately high vapor pressure. Other copper compounds, for example (1,1,1,5,5,5-hexafluoro-2,4-pentanedioonate) CuL, where L is 1,5-cyclooctadiene (CUD), alkyne or Trialkylphosphine) is a solid or liquid having a low vapor pressure. Although (hfac) Cu (trimethylvinylsilane) ((hfac) Cu (tmvs)) is the most used copper precursor, its stability is not satisfactory for the selective growth of reproducible copper films. In addition, research has demonstrated that the chemical vapor deposition reaction of (hfac) Cu (tmvs) under ultrahigh vacuum conditions produced contamination by carbon and fluorine in the deposited film. Thus, precursors with high volatility and stability that do not contain fluorinated ligands are more preferred in the deposition of copper by CVD.

Copper compounds of acetoacetate derivatives that do not contain fluorinated ligands have previously been used as CVD precursors. These compounds have been reported to be volatile at low substrate temperatures and to deposit copper films, but the acetoacetate derivatives studied have been found to be attractive because they are volatile without the use of fluorinated ligands and deposit copper films at temperatures below 200 ° C. However, these derivatives are solids with high melting points and no selective deposition of copper is possible. Cu (I) acetoacetate derivatives, on the other hand, deposited copper films at relatively low temperatures through disproportionation. However, only a few are practical for use as CVD precursors because they are solid or liquid with low vapor pressure, or have very low thermal stability (ie their decomposition temperature is within a few degrees C of their vaporization temperature).

As a result, there is a need for organometallic precursors that deposit metal films without degradation of ligands and without associated toxic byproducts.

<Overview of invention>

Novel precursor compositions for metal film deposition are disclosed herein. Generally disclosed compositions use precursor compounds including copper, gold, silver, and the like. More specifically, the disclosed precursor compounds use pentadienyl ligands coupled to metals (eg, copper, gold, silver) to increase thermal stability. Also, deposition of copper, gold or silver is disclosed with the use of other precursors to deposit metal films. The methods and compositions can be used in a variety of deposition methods. The disclosed compounds have several advantages, such as thermal stability at room temperature. In addition, the disclosed precursors do not contain toxic phosphorus compounds. Other aspects of the methods and compositions will be described in more detail below.

In one embodiment, a method of depositing a metal film on one or more substrates includes providing one or more substrates in a reaction chamber. The method further includes introducing a first precursor into the reaction chamber, wherein the first precursor comprises an organometallic compound represented by the formula (Op) _x (Cp) _y MR ′ _2-xy . M is a Group 11 metal. Op is ring-opening-pentadienyl group, Cp is cyclopentadienyl group, R 'is C1 to C12 alkyl group, trialkylsilyl group, alkylamide group, alkoxide group, alkylsilyl group, alkylsilylamide group, amidinate group , CO, SMe ₂ , SEt ₂ , SiPr ₂ , SMeEt, SMe (iPr), SEt (iPr), OMe ₂ , OEt ₂ , tetrahydrofuran (THF) and combinations thereof. The Op group and the Cp group may include a functional group selected from the group consisting of a hydrogen group, a halogen group, a C1 to C4 alkyl group, an alkylamide group, an alkoxide group, an alkylsilylamide group, an amidinate group, a carbonyl group, and a combination thereof. Subscript "x" is an integer ranging from 0 to 1, and subscript "y" is an integer ranging from 0 to 1. The method also includes vaporizing the first precursor to deposit a metal film on one or more substrates.

In one embodiment, the precursor for depositing a metal film on one or more substrates comprises an organometallic compound represented by the formula (Op) _x (Cp) _y MR ′ _2-xy , wherein M is a Group 11 metal, Op is ring-opening-pentadienyl group, Cp is cyclopentadienyl group, R 'is C1 to C12 alkyl group, trialkylsilyl group, alkylamide group, alkoxide group, alkylsilyl group, alkylsilylamide group, amidinate group , CO, SMe ₂ , SEt ₂ , SiPr ₂ , SMeEt, SMe (iPr), SEt (iPr), OMe ₂ , OEt ₂ , tetrahydrofuran (THF) and combinations thereof. The Op group and the Cp group may include a functional group selected from the group consisting of a hydrogen group, a halogen group, a C1 to C4 alkyl group, an alkylamide group, an alkoxide group, an alkylsilylamide group, an amidinate group, a carbonyl group, and a combination thereof. Subscript x is an integer ranging from 0 to 1, and subscript y is an integer ranging from 0 to 1.

The foregoing has outlined rather broadly the features and technical advantages of the present invention in order that the detailed description of the invention that follows may be better understood. Further features and advantages of the present invention which form the subject matter of the present invention will be described later. Those skilled in the art will appreciate that the conception and specific embodiments disclosed may be readily utilized as a basis for modifying or designing other structures for carrying out the same purposes of the present invention. Moreover, those skilled in the art will recognize that such equivalent constructions do not depart from the spirit and scope of the invention as described in the appended claims.

Notation and Nomenclature

Certain terms have been used to refer to specific system components throughout the following description and claims. This document is not intended to distinguish between components that differ in name but serve the same function.

In the following discussion and claims, the terms "including" and "comprising" have been used in an open termination manner and are therefore to be interpreted to mean "including, but not limited to". In addition, the term "coupling" is intended to mean an indirect or direct chemical bond. Thus, when the first molecule couples to the second molecule, this linkage may be by direct bonds or by indirect bonds through other functional groups or bonds. The bond can be any known chemical bond, such as, but not limited to, covalent, ionic, electrostatic, dipole-dipole bonds, and the like.

The term "alkyl group" as used herein denotes a saturated functional group containing only carbon and hydrogen atoms. The term "alkyl group" also denotes a linear, branched or cyclic alkyl group. Examples of linear alkyl groups include, but are not limited to, methyl groups, ethyl groups, propyl groups, butyl groups, and the like. Examples of branched alkyl groups include, but are not limited to, t -butyl. Examples of cyclic alkyl groups include, but are not limited to, cyclopropyl groups, cyclopentyl groups, cyclohexyl groups, and the like.

As used herein, the abbreviation "Me" represents a methyl group, the abbreviation "Et" represents an ethyl group, the abbreviation "Pr" represents a propyl group, and the abbreviation "iPr" represents an isopropyl group.

In one embodiment, the precursor for metal film deposition comprises an organometallic compound represented by the formula (Op) _x (Cp) _y MR ′ _2-xy . The term "organic metal" as used herein may refer to a compound or molecule containing a metal-carbon bond. M can be any suitable metal. In particular, M may include, but is not limited to, any Group 11 metal, such as copper (Cu), silver (Ag), or gold (Au). Other suitable metals include ruthenium or tantalum. Op is a substituted or unsubstituted ring-openedenyl group ligand. In addition, Cp is a cyclopentadienyl ligand and may or may not be substituted. Subscript x is an integer ranging from 0 to 1 representing the number of Op ligands. Subscript y is an integer ranging from 0 to 1 representing the number of Cp ligands.

The R ′ substituent may be a functional group providing an even number of π electrons. Specifically, R 'may be a C1 to C12 linear or branched alkyl group. Further, R 'is trialkylsilyl group, alkyl group, alkylamide group, alkoxide group, alkylsilyl group, alkylsilylamide group, amidinate group, CO, SiMe ₂ , SiEt ₂ , SiPr ₂ , SiMeEt, SiMe (iPr ), SiEt (iPr), OMe ₂ , OEt ₂ , tetrahydrofuran (THF) or a combination thereof. In embodiments in which the organometallic compound comprises more than one R 'group, each R' group coupled to M may be the same or different from each other. In an exemplary embodiment, R 'is bis ((trimethylsilyl) acetylene Other examples of suitable R' groups are butadiene, butane, acetylene, cyclohexadiene, trimethylsilylacetylene, cyclohexa-1,4-diene, propylene , Ethylene and the like, but are not limited thereto.

According to one embodiment, the Cp ligand can be represented by the formula:

Alternatively, the Cp ligand can be represented by the formula CpR ^1-5 . R ¹ to R ⁵ are each independently a hydrogen group, a halogen group (eg, Cl, Br, etc.), a C1 to C4 linear or branched alkyl group, an alkylamide group, an alkoxide group, an alkylsilylamide group, an amidinate group , Carbonyl group or a combination thereof. R ¹ to R ⁵ may be the same or different from each other. Examples of suitable Cp ligands include, but are not limited to, methylcyclopentadiene, ethylcyclopentadiene, isopropylcyclopentadiene, and combinations thereof. In one or more embodiments, at least four of R ¹ to R ⁵ of the Cp ligand represented by Formula 1 are hydrogen groups (ie, unsubstituted).

In one embodiment, the Op ligand can be represented by the formula:

Op ligands may alternatively be represented by the formula OpR ^1-7 . R ¹ to R ⁷ are each independently a hydrogen group, a halogen group (eg, Cl, Br, etc.), a C1 to C4 linear or branched alkyl group, an alkylamide group, an alkoxide group, an alkylsilylamide group, an amidinate group , Carbonyl group or a combination thereof. R ¹ to R ⁷ may be the same or different from each other. Examples of Op ligands are 1,3-pentadiene, 1,4-pentadiene, 3-methyl-1,3-pentadiene, 3-methyl-1,4-pentadiene, 2,4-dimethyl-1,3 -Pentadiene, 2,4-dimethyl-1,4-pentadiene, 3-ethyl-1,3-pentadiene, 1,5-bistrimethoxysilyl-1,3-pentadiene, 1,5-bis Trimethoxysilyl-1,4-pentadiene and combinations thereof. In one or more embodiments, at least 5 of R ¹ to R ⁷ of the Op ligands represented by Formula 2 are hydrogen groups (ie, unsubstituted).

In one embodiment, the precursor may be an organometallic compound represented by the formula:

In this embodiment, y is zero. That is, the organometallic compound includes only open pentadienyl ligands and R 'ligands. Also, in one or more embodiments, at least 5 of R ¹ to R ⁷ are hydrogen groups. In other words, the Op group has two substituents in addition to the MR ′ functional group. Two substituents are preferably a methyl group or an ethyl group. In one or more embodiments, the precursor is represented by the formula shown in Formula 3 wherein R 'is bis ((trimethylsilyl) acetylene.

In one embodiment, the precursor may be an organometallic compound represented by the formula:

In this embodiment, x is zero. That is, the organometallic compound includes only cyclopentadienyl ligand and R 'ligand. Also, in one or more embodiments, at least four of R ¹ to R ⁵ are hydrogen groups. That is, the Cp group has only a single substituent in addition to the MR 'functional group. The single substituent is preferably a methyl group or an ethyl group. In one or more embodiments, the precursor has the formula represented by Formula 4, wherein R 'is bis ((trimethylsilyl) acetylene.

In general, the disclosed metal precursors have a low melting point. In one or more embodiments, the metal precursor is a liquid at room temperature (eg, ˜25 ° C.). In particular embodiments of the precursor may have a melting point of less than about 50 ° C., alternatively less than about 40 ° C., alternatively less than about 35 ° C.

Examples of disclosed precursors containing Cu include CuCp (ethylene), Cu (MeCp) (ethylene), Cu (EtCp) (ethylene), Cu (iPrCp) (ethylene), CuCp (propylene), Cu (MeCp) (propylene) Cu (EtCp) (propylene), Cu (iPrCp) (propylene), CuCp (1-butene), Cu (MeCp) (1-butene), Cu (EtCp) (1-butene), Cu (iPrCp) (2 -Butene), CuCp (2-butene), Cu (MeCp) (2-butene), Cu (EtCp) (2-butene), Cu (iPrCp) (2-butene), CuCp (butadiene), Cu (MeCp) (Butadiene), Cu (EtCp) (butadiene), Cu (iPrCp) (butadiene), CuCp (cyclobutadiene), Cu (MeCp) (cyclobutadiene), Cu (EtCp) (cyclobutadiene), Cu (iPrCp) (cyclo Butadiene), CuCp (cyclohexa-1,3-ene), Cu (MeCp) (cyclohexa-1,3-diene), Cu (EtCp) (cyclohexa-1,3-diene), Cu (iPrCp) ( Cyclohexan-1,3-diene), CuCp (cyclohexa-1,4-diene), Cu (MeCp) (cyclohexa-1,4-diene), Cu (EtCp) (cyclohexa-1,4-diene ), Cu (iPrCp) (cyclohexa-1,4-diene), CuCp (acetylene), Cu (MeCp) (acetylene), Cu (EtCp) (acetylene), Cu (iPrCp) (acetylene), CuCp (tree Methylsilylacetylene), Cu (MeCp) (trimethylsilyl acetylene), Cu (EtCp) (trimethylsilylacetylene), Cu (iPrCp) (trimethylsilylacetylene), CuCp (bis (trimethylsilyl) acetylene), Cu (MeCp) ( Trimethylsilylacetylene), Cu (EtCp) (bis (trimethylsilyl) acetylene), Cu (iPrCp) (bis (trimethylsilyl) acetylene), CuCp (ethylene), Cu (MeCp) (ethylene), Cu (EtCp) (ethylene ), Cu (iPrCp) (ethylene), CuCp (trimethylvinylsilane), Cu (MeCp) (trimethylvinylsilane), Cu (EtCp) (trimethylvinylsilane), Cu (iPrCp) (trimethylvinylsilane), CuCp (bis (Trimethylsilyl) acetylene), Cu (MeCp) (bis (trimethylsilyl) ethylene), Cu (EtCp) (bis (trimethylsilyl) ethylene), Cu (iPrCp) (bis (trimethylsilyl) ethylene), Cu (2, 4-dimethylpentadienyl) (ethylene), Cu (2,4-dimethylpentadienyl) (propylene), Cu (2,4-dimethylpentadienyl) (1-butylene), Cu (2,4- Dimethylpentadienyl) (2-butylene), Cu (2,4-dimethylpentadienyl) (butadiene), Cu (2,4-di Tilpentadienyl) (cyclobutadiene), Cu (2,4-dimethylpentadienyl) (cyclohexa-1,3-diene), Cu (2,4-dimethylpentadienyl) (cyclohexa-1,4 -Diene), Cu (2,4-dimethylpentadienyl) (acetylene), Cu (2,4-dimethylpentadienyl) (trimethylsilylacetylene), Cu (2,4-dimethylpentadienyl) (bis ( Trimethylsilyl) acetylene), or combinations thereof.

Examples of disclosed precursors containing Ag include AgCp (ethylene), Ag (MeCp) (ethylene), Ag (EtCp) (ethylene), Ag (iPrCp) (ethylene), AgCp (propylene), Ag (MeCp) (propylene) Ag (EtCp) (propylene), Ag (iPrCp) (propylene), AgCp (1-butene), Ag (MeCp) (1-butene), Ag (EtCp) (1-butene), Ag (iPrCp) (2 -Butene), AgCp (2-butene), Ag (MeCp) (2-butene), Ag (EtCp) (2-butene), Ag (iPrCp) (2-butene), AgCp (butadiene), Ag (MeCp ) (Butadiene), Ag (EtCp) (butadiene), Ag (iPrCp) (butadiene), AgCp (cyclobutadiene), Ag (MeCp) (cyclobutadiene), Ag (EtCp) (cyclobutadiene), Ag (iPrCp) ( Cyclobutadiene), AgCp (cyclohexa-1,3-diene), Ag (MeCp) (cyclohexa-1,3-diene), Ag (EtCp) (cyclohexa-1,3-diene), Ag (iPrCp) (Cyclohexa-1,3-diene), AgCp (cyclohexa-1,4-diene), Ag (MeCp) (cyclohexa-1,4-diene), Ag (EtCp) (cyclohexa-1,4- Diene), Ag (iPrCp) (cyclohexa-1,4-diene), AgCp (acetylene), Ag (MeCp) (acetylene), Ag (EtCp) (acetylene), Ag (iPrCp) (acetylene), AgCp ( Limethylsilylacetylene), Ag (MeCp) (trimethylsilylacetylene), Ag (EtCp) (trimethylsilylacetylene), Ag (iPrCp) (trimethylsilylacetylene), AgCp (bis (trimethylsilyl) acetylene), Ag (MeCp) (Bis (trimethylsilyl) ethylene), Ag (EtCp) (bis (trimethylsilyl) acetylene), Ag (iPrCp) (bis (trimethylsilyl) acetylene), AgCp (trimethylvinylsilane), Ag (MeCp) (trimethylvinylsilane ), Ag (EtCp) (trimethylvinylsilane), Ag (iPrCp) (trimethylvinylsilane), AgCp (bis (trimethylsilyl) acetylene), Ag (MeCp) (bis (trimethylsilyl) ethylene), Ag (EtCp) ( Bis (trimethylsilyl) ethylene), Ag (iPrCp) (bis (trimethylsilyl) ethylene), Ag (2,4-dimethylpentadienyl) (ethylene), Ag (2,4-dimethylpentadienyl) (propylene) , Ag (2,4-dimethylpentadienyl) (1-butylene), Ag (2,4-dimethylpentadienyl) (2-butylene), Ag (2,4-dimethylpentadienyl) (butadiene ), Ag (2,4-dimethylpentadienyl) (cyclobutadiene), Ag (2,4-dimethylpentadien Nyl) (cyclohexadi-1,3-ene), Ag (2,4-dimethylpentadienyl) (cyclohexadi-1,4-ene), Ag (2,4-dimethylpentadienyl) (acetylene ), Ag (2,4-dimethylpentadienyl) (trimethylsilylacetylene), Ag (2,4-dimethylpentadienyl) (bis (trimethylsilyl) acetylene) or combinations thereof, including but not limited to no.

Examples of disclosed precursors containing Au are AuCp (ethylene), Au (MeCp) (ethylene), Au (EtCp) (ethylene), Au (iPrCp) (ethylene), AuCp (propylene), Au (MeCp) (propylene) Au (EtCp) (propylene), Au (iPrCp) (propylene), AuCp (1-butene), Au (MeCp) (1-butene), Au (EtCp) (1-butene), Au (iPrCp) (2 -Butene), AuCp (2-butene), Au (MeCp) (2-butene), Au (EtCp) (2-butene), Au (iPrCp) (2-butene), AuCp (butadiene), Au (MeCp) (Butadiene), Au (EtCp) (butadiene), Au (iPrCp) (butadiene), AuCp (cyclobutadiene), Au (MeCp) (cyclobutadiene), Au (EtCp) (cyclobutadiene), Au (iPrCp) (cyclo Butadiene), AuCp (cyclohexa-1,3-diene), Au (MeCp) (cyclohexa-1,3-diene), Au (EtCp) (cyclohexa-1,3-diene), Au (iPrCp) ( Cyclohexan-1,3-diene), AuCp (cyclohexa-1,4-diene), Au (MeCp) (cyclohexa-1,4-diene), Au (EtCp) (cyclohexa-1,4-diene ), Au (iPrCp) (cyclohexa-1,4-diene), AuCp (acetylene), Au (MeCp) (acetylene), Au (EtCp) (acetylene), Au (iPrCp) (acetylene), AuCp (t Methylsilylacetylene), Au (MeCp) (trimethylsilylacetylene), Au (EtCp) (trimethylsilylacetylene), Au (iPrCp) (trimethylsilylacetylene), AuCp (bis (trimethylsilyl) acetylene), Au (MeCp) ( Bis (trimethylsilyl) ethylene), Au (EtCp) (bis (trimethylsilyl) acetylene), Au (iPrCp) (bis (trimethylsilyl) acetylene), AuCp (trimethylvinylsilane), Au (MeCp) (trimethylvinylsilane) Au (EtCp) (trimethylvinylsilane), Au (iPrCp) (trimethylvinylsilane), AuCp (bis (trimethylsilyl) acetylene), Au (MeCp) (bis (trimethylsilyl) ethylene), Au (EtCp) (bis (Trimethylsilyl) ethylene), Au (iPrCp) (bis (trimethylsilyl) ethylene), Au (2,4-dimethylpentadienyl) (ethylene), Au (2,4-dimethylpentadienyl) (propylene), Au (2,4-dimethylpentadienyl) (1-butylene), Au (2,4-dimethylpentadienyl) (2-butylene), Au (2,4-dimethylpentadienyl) (butadiene) , Au (2,4-dimethylpentadienyl) (cyclobutadiene), Au (2,4-dimethylpentadiene ) (Cyclohexadi-1,3-ene), Au (2,4-dimethylpentadienyl) (cyclohexadi-1,4-ene), Au (2,4-dimethylpentadienyl) (acetylene) , Au (2,4-dimethylpentadienyl) (trimethylsilylacetylene), Au (2,4-dimethylpentadienyl) (bis (trimethylsilyl) acetylene) or combinations thereof .

The disclosed precursor compounds can be deposited using any deposition method known to those skilled in the art. Examples of suitable deposition methods include conventional CVD, low pressure chemical vapor deposition (LPCVD), atomic layer deposition (ALD), pulsed chemical vapor deposition (P-CVD), plasma enhanced atomic layer deposition (PE-ALD), or a combination thereof, It is not limited to this. In one embodiment, the first precursor may be introduced into the reaction chamber. The reaction chamber is a device in which deposition is carried out under conditions suitable for reacting precursors to form layers, for example cold-wall type reactors, hot-wall type reactors, single wafer reactors, multiple It can be, but is not limited to, any enclosure or chamber in a wafer reactor or other type of deposition system. The first precursor can be introduced into the reaction chamber by bubbling an inert gas (eg, N ₂ , He, Ar, etc.) with the precursor and providing a mixture of the inert gas and the precursor to the reactor.

Generally, the reaction chamber contains one or more substrates onto which a metal layer or film will be deposited. One or more substrates may be any suitable substrate used for semiconductor manufacturing. Examples of suitable substrates include, but are not limited to, silicon substrates, silica substrates, silicon nitride substrates, silicon oxynitride substrates, tungsten substrates, or combinations thereof. In addition, substrates comprising tungsten or precious metals (eg, platinum, palladium, rhodium or gold) can be used.

In one embodiment, the method of depositing a metal film on a substrate can further include introducing a second precursor into the reaction chamber. The second precursor may be a metal precursor containing at least one metal other than the Group 11 metal. For example, the second precursor may include, but is not limited to, Mg, Ca, Zn, B, Al, In, Si, Ge, Sn, Ti, Zr, Hf, V, Nb, Ta, or a combination thereof. It is not. Other examples of metals include rare earth metals and lanthanum based elements. The second precursor may contain silicon and / or germanium. In particular, examples of suitable second metal precursors include trisilylamine, silane, disilane, trisilane, bis (tert-butylamino) silane (BTBAS), bis (diethylamino) silane (BDEAS) or combinations thereof However, it is not limited thereto. In addition, the second metal precursor may be an aminosilane represented by the formula SiH _x (NR ¹ R ² ) _4-x . Subscript x is an integer from 0 to 4. R ¹ and R ² may each independently be a hydrogen group or a linear, branched or cyclic C 1 to C 6 alkyl group. R ¹ and R ² may be the same or different from each other. In one embodiment, the second metal precursor is tris (diethylamino) silane (TriDMAS).

In an alternative embodiment, the second precursor can be an aluminum source. Examples of suitable aluminum sources include, but are not limited to, trimethylaluminum, dimethylaluminum hydride or combinations thereof. The aluminum source may also be amidoalan represented by the formula AlR ¹ _x (NR ² R ³ ) _3-x . Subscript x is an integer from 0 to 3. R ¹ , R ² and R ³ may each independently be a hydrogen group or a linear, branched or cyclic C 1 to C 6 carbon chain, which may be the same or different from each other.

In another embodiment, the second precursor is tantalum selected from the group comprising MCl ₅ and corresponding adducts, M (NMe ₂ ) ₅ , M (NEt ₂ ) ₄ , M (NEt ₂ ) _5, or combinations thereof And / or a niobium source. M represents tantalum or niobium. The tantalum and / or niobium source may also be an amino containing tantalum and / or niobium source represented by the formula M (= NR ¹ ) (NR ² R ³ ) ₃ . R ¹ , R ² and R ³ may each independently be a hydrogen group or a linear, branched or cyclic C 1 to C 6 alkyl group. Generally, the weight ratio of first metal precursor to cobalt precursor introduced into the reaction chamber is about 100: 1 to about 1: 100, alternatively about 50: 1 to about 1:50, alternatively about 1: 1 to about 10: 1. It may be in the range of.

, OH

, N

, NH

, NH₂

또는 이들의 조합물을 포함하되, 이에 제한되는 것은 아니다. 추가 실시양태에서, 불활성 기체를 반응 챔버에 도입할 수 있다. 불활성 기체의 예는 He, Ar, Ne 또는 이들의 조합물을 포함하되, 이에 제한되는 것은 아니다. 환원 유체도 반응 챔버에 도입할 수 있다. 적합한 환원 유체의 예는 일산화탄소, Si₂Cl₆ 또는 이들의 조합물을 포함하되, 이에 제한되는 것은 아니다.In an embodiment, the reaction chamber can be maintained at a pressure ranging from about 1 Pa to about 100,000 Pa, alternatively from about 10 Pa to about 10,000 Pa, alternatively from about 25 Pa to about 1000 Pa. In addition, the temperature in the reaction chamber may range from about 100 ° C. to about 500 ° C., alternatively from about 120 ° C. to about 450 ° C., alternatively from about 150 ° C. to about 350 ° C. In addition, deposition of the metal film can be carried out in the presence of a hydrogen source. Thus, a hydrogen source can be introduced into the reaction chamber. The hydrogen source can be a fluid or a gas. Examples of suitable hydrogen sources are H ₂ , H ₂ O, H ₂ O ₂ , N ₂ , NH ₃ , hydrazine and their alkyl or aryl derivatives, diethylsilane, trisilylamine, silane, disilane, phenylsilane and Si- Any molecule containing an H bond, dimethylaluminum hydride, a hydrogen containing radical such as H

, OH

, N

, NH

, NH ₂

Or combinations thereof, but is not limited thereto. In further embodiments, an inert gas can be introduced into the reaction chamber. Examples of inert gases include, but are not limited to, He, Ar, Ne, or combinations thereof. Reducing fluid can also be introduced into the reaction chamber. Examples of suitable reducing fluids include, but are not limited to, carbon monoxide, Si ₂ Cl _6, or combinations thereof.

The metal precursors can be introduced into the reaction chamber sequentially (as in ALD) or simultaneously (as in CVD). In one embodiment, the first and second precursors can be pulsed into the reaction chamber sequentially or simultaneously (eg, pulsed CVD) while continuously introducing oxidizing or nitriding gas into the reaction chamber. Each pulse of cobalt and / or first metal precursor may last for a time ranging from about 0.01 seconds to about 10 seconds, alternatively from about 0.3 seconds to about 3 seconds, alternatively from about 0.5 seconds to about 2 seconds. In another embodiment, the reaction fluid and / or inert gas may also be pulsed into the reaction chamber. In such embodiments, the pulse of each gas may last for a time ranging from about 0.01 seconds to about 10 seconds, alternatively from about 0.3 seconds to about 3 seconds, alternatively from about 0.5 seconds to about 2 seconds.

While embodiments of the invention have been shown and described, modifications thereof can be made by those skilled in the art without departing from the spirit and teachings of the invention. The described embodiments and the examples provided herein are illustrative only and are not intended to be limiting. Various modifications and variations of the invention disclosed herein are possible and are within the scope of the invention. Accordingly, the scope of protection is not limited by the description set forth above, but only by the following claims, and includes all equivalents of the claimed subject matter.

The discussion of references, particularly any references published after the priority date of the present application, does not recognize it as a prior art for the present invention. The disclosures of all patents, patent applications, and publications cited herein are hereby incorporated by reference in their entirety to the extent that they provide illustrations, procedures, or other details in addition to those set forth herein.

Claims (32)

a) providing at least one substrate in a reaction chamber; b) Formula (Op) _x (Cp) _y MR ' _2-xy (wherein M is a Group 11 metal, Op is a ring-opening-pentadienyl group, Cp is a cyclopentadienyl group, and R' is C1 to C12) Alkyl group, trialkylsilyl group, alkylamide group, alkoxide group, alkylsilyl group, alkylsilylamide group, amidinate group, CO, SMe ₂ , SEt ₂ , SiPr ₂ , SiMeEt, SiMe (iPr), SiEt (iPr) , OMe ₂ , OEt ₂ , tetrahydrofuran (THF) and combinations thereof, Op and Cp each represent a hydrogen group, a halogen group, a C1 to C4 alkyl group, an alkylamide group, an alkoxide group, an alkylsilylamide Organometallic compound represented by the group consisting of a group consisting of a group, an amidate group, a carbonyl group, and combinations thereof, wherein x is an integer ranging from 0 to 1, and y is an integer ranging from 0 to 1. Introducing a first precursor comprising a into the reaction chamber; And c) vaporizing the first precursor to deposit a metal film on the one or more substrates And depositing a metal film on one or more substrates. The method of claim 1, further comprising introducing a second precursor into the reaction chamber. The method of claim 2, wherein the second precursor is Mg, Ca, Zn, B, Al, In, Si, Ge, Sn, Ti, Zr, Hf, V, Nb, Ta, lanthanum-based elements, rare earth metals or combinations thereof How to include. The method of claim 2, wherein the second precursor is trisilylamine, silane, disilane, trisilane, bis (tert-butylamino) silane (BTBAS), bis (diethylamino) silane (BDEAS), formula SiH _x (NR ¹ R ² ) _4-x (wherein x is an integer from 0 to 4, R ¹ and R ² are each independently a hydrogen group or a C1 to C6 alkyl group, and R ¹ and R ² may be the same as or different from each other; Aminosilane represented by the above) or combinations thereof. The method of claim 2, wherein the second precursor is an aluminum source. The method of claim 5, wherein the aluminum source is trimethylaluminum, dimethylaluminum hydride, formula AlR ¹ _x (NR ² R ³ ) _3-x , wherein x is an integer from 0 to 3, and R ¹ , R ² and R ³ may each independently be a hydrogen group or a C1 to C6 alkyl group, and R ¹ , R ² and R ³ may each be the same or different from each other), or a combination thereof. The method of claim 2, wherein the second precursor comprises a tantalum source or niobium source. The method of claim 7, wherein the tantalum source or niobium source is of formula MCl ₅ , M (NMe ₂ ) ₅ , M (NEt ₂ ) ₄ , M (NEt ₂ ) ₅ , M (= NR ¹ ) (NR ² R ³ ) ₃ (Wherein R ¹ , R ² and R ³ may each independently be a hydrogen group or a C1 to C6 alkyl group, R ¹ , R ² and R ³ may be the same or different from each other, and M is tantalum or niobium) And at least one compound represented by &quot; The method of claim 2, wherein introducing the first precursor and the second precursor into the reaction chamber is performed simultaneously. The method of claim 2, wherein introducing the first precursor and the second precursor into the reaction chamber is performed sequentially. The method of claim 1, wherein introducing the first precursor and the second precursor into the reaction chamber comprises pulsing the first metal precursor and the second metal precursor into the reaction chamber. The method of claim 1 wherein M is gold, silver or copper. The method of claim 1 wherein the first precursor is a liquid at room temperature. The method of claim 1, wherein the first precursor is represented by the formula:

In formula, five or more of R <^1> -R <^7> is a hydrogen group, and two of R <^1> -R <^7> contains a methyl group or an ethyl group. The method of claim 1, wherein the first precursor is represented by the formula: In the formula, at least four of R ¹ to R ⁵ are hydrogen groups, and at least one of R ¹ to R ⁵ contains a methyl group or an ethyl group. The process of claim 1 wherein the first precursor is MCp (ethylene), M (MeCp) (ethylene), M (Cp) (ethylene), M (iPrCp) (ethylene), MCp (propylene), M (MeCp) (propylene ), M (EtCp) (propylene), M (iPrCp) (propylene), MCp (1-butene), M (MeCp) (1-butene), M (EtCp) (1-butene), M (iPrCp) ( 2-butene), MCp (2-butene), M (MeCp) (2-butene), M (EtCp) (2-butene), M (iPrCp) (2-butene), MCp (butadiene), M ( MeCp) (butadiene), M (EtCp) (butadiene), M (iPrCp) (butadiene), MCp (cyclobutadiene), M (MeCp) (cyclobutadiene), M (EtCp) (cyclobutadiene), M (iPrCp) (Cyclobutadiene), MCp (cyclohexa-1,3-diene), M (MeCp) (cyclohexa-1,3-diene), M (EtCp) (cyclohexa-1,3-diene), M (iPrCp ) (Cyclohexa-1,3-diene), MCp (cyclohexa-1,4-diene), M (MeCp) (cyclohexa-1,4-diene), M (EtCp) (cyclohexa-1,4 Dienes), M (iPrCp) (cyclohexa-1,4-diene), MCp (acetylene), M (MeCp) (acetylene), M (EtCp) (acetylene), M (iPrCp) (acetylene), MCp ( Trimethylsilylacetylene), M (MeCp) (trime Tylsilylacetylene), M (EtCp) (trimethylsilylacetylene), M (iPrCp) (trimethylsilylacetylene), MCp (bis (trimethylsilyl) acetylene), M (MeCp) (bis (trimethylsilyl) ethylene), M ( EtCp) (bis (trimethylsilyl) acetylene), M (iPrCp) (bis (trimethylsilyl) acetylene), MCp (trimethylvinylsilane), M (MeCp) (trimethylvinylsilane), M (EtCp) (trimethylvinylsilane) , M (iPrCp) (trimethylvinylsilane), MCp (bis (trimethylsilyl) acetylene), M (MeCp) (bis (trimethylsilyl) ethylene), M (EtCp) (bis (trimethylsilyl) ethylene), M (iPrCp) (bis (trimethylsilyl) ethylene), M (2,4-dimethylpentadienyl) (ethylene), M (2,4-dimethylpentadienyl) (propylene), M (2,4-dimethylpenta Dienyl) (1-butylene), M (2,4-dimethylpentadienyl) (2-butylene), M (2,4-dimethylpentadienyl) (butadiene), M (2,4-dimethyl Pentadienyl) (cyclobutadiene), M (2,4-dimethylpentadienyl) (cyclohexadi-1,3-ene), M (2,4-dimethylpentadienyl) ( Chlohexadi-1,4-ene), M (2,4-dimethylpentadienyl) (acetylene), M (2,4-dimethylpentadienyl) (trimethylsilylacetylene), M (2,4-dimethyl Pentadienyl) (bis (trimethylsilyl) acetylene) or a combination thereof, wherein M is Au, Ag or Cu. The method of claim 1, further comprising introducing a hydrogen source, a reducing fluid, an inert gas, or a combination thereof into the reaction chamber. 18. The process of claim 17 wherein the hydrogen source is H ₂ , H ₂ O, H ₂ O ₂ , N ₂ , NH ₃ , hydrazine and alkyl or aryl derivatives thereof, diethylsilane, trisilylamine, silane, disilane, phenylsilane Dimethylaluminum hydride, H

Radical, OH

Radicals, NH

Radicals, NH ₂

And radicals or combinations thereof. The method of claim 17, wherein the reducing fluid comprises carbon monoxide, Si ₂ Cl _6, or a combination thereof. The method of claim 1, wherein the at least one substrate comprises silicon, silica, silicon nitride, silicon oxynitride, tungsten, or a combination thereof. The method of claim 1, wherein the temperature of the reaction chamber ranges from about 150 ° C. to about 350 ° C. in step (c). The process of claim 1 wherein the pressure in the reaction chamber is in a range from about 1 Pa to about 1,000 Pa in step (c). A precursor for depositing a metal film on a substrate, comprising an organometallic compound represented by the following formula: (Op) _x (Cp) _y MR ' _2-xy Wherein M is a Group 11 metal, Op is a ring-openedadienyl group, Cp is a cyclopentadienyl group, R 'is a C1-C12 alkyl group, a trialkylsilyl group, an alkylamide group, an alkoxide group, an alkylsilyl group , Alkylsilylamide group, amidinate group, CO, SiMe ₂ , SiEt ₂ , SiPr ₂ , SiMeEt, SiMe (iPr), SiEt (iPr), OMe ₂ , OEt ₂ , tetrahydrofuran (THF) and combinations thereof Op and Cp are each selected from the group consisting of hydrogen group, halogen group, C1 to C4 alkyl group, alkylamide group, alkoxide group, alkylsilylamide group, amidinate group, carbonyl group and combinations thereof Functional groups selected from, x is an integer ranging from 0 to 1, and y is an integer ranging from 0 to 1. The method of claim 23, wherein M is copper, gold or silver. The method of claim 23, wherein x is 1 and y is 0. The method of claim 23, wherein y is 1 and x is 0. The method according to claim 23, wherein Op is a formula OpR ^1-7 (wherein R ¹ to R ⁷ are each independently a hydrogen group, a halogen group, a C1 to C4 alkyl group, an alkylamide group, an alkoxide group, an alkylsilylamide group, an Midiate group, carbonyl group, or a combination thereof, and R ¹ to R ⁷ may be the same or different from each other. The method according to claim 23, wherein Cp is a formula CpR ^1-5 (wherein R ¹ to R ⁵ are each independently a hydrogen group, a halogen group, a C1 to C4 alkyl group, an alkylamide group, an alkoxide group, an alkylsilylamide group, Midinate group, carbonyl group, or a combination thereof, and R ¹ to R ⁵ may be the same or different from each other. 24. The method of claim 23, wherein R 'is bis (trimethylsilyl) acetylene. The compound according to claim 23, wherein R 'is trialkylsilyl group, alkyl group, alkylamide group, alkoxide group, alkylsilyl group, alkylsilylamide group, amidinate group, CO, SiMe ₂ , SiEt ₂ , SiPr ₂ , SiMeEt, SiMe (iPr), SiEt (iPr), OMe ₂ , OEt ₂ , tetrahydrofuran (THF) or a combination thereof. The method of claim 23, wherein R ′ comprises butadiene, butane, acetylene, cyclohexadiene, trimethylsilylacetylene, cyclohexa-1,4-diene, propylene or ethylene. The precursor of claim 23 wherein the organometallic compound has a melting point of less than about 35 ° C. 25.